Hydroxyethylamino-derivatives of the anthraquinone series and process of making same



Patented May 30, 1933 UNITED STATES PATENT- F ICE HERMANN nAUsEE' m'mx BoiIMEE, or IBASEL, SWITZERLAND, AssIGnoEs To THE Emu SOCIETY or CHEMICAL INDUSTRY IN BASLE, or BASEL, SWITZERLAND nYDEoxYETHYLAMmo-nEnIvATrvEs OF "THE ANTHRAQ'UINONE 1111) PROCESS or MAKING SAME I I No Drawing. Application riled May 26, 1931, Serial No. 540,208, and. in Switzerland June 4,1930.

The present invention relates to the manufacture of hydroxyethylamino-derivatives of the anthraquinone series. It comprises the process of making these derivatives and the '5 derivatives themselves.

It is'known, that hydroxyethylamino-des rivatives of the anthraquinone series maybe made by condensing the corresponding leucohydroxy-compounds with mono-ethanolamine andsubsequently oxidizin the conden sation product thus formed compare, for example, British Specification No. 289,807, Examples 3 and 4). The subsequent oxidation is best performed by means of an oxi- 15 dizing agent, such as nitrobenzene or benzoyl peroxide in some cases with the addition of a catalyst (compare German Specification No. 488,684 and British Specification No. 270,779).

According to this invention the leuco-compounds which are obtained by condensing leuco 1 :4 dihydroxyanthraquinones with mono-ethanolamine, that is to say the produ'ctsof the general formula I OH NH-CIHA-OH wherein m in both cases stands for H or OH, have the pecularity that when heatedwith an excess of concentrated mono-ethanolamine orfurther products of the reaction of ethylene-oxide with ammonia (dior triethanolamine or mixtures of mono-, di and tri-" ethanolamine), with access of air, they are 40 oxidized smoothly to anthraquinone derivatives. The isolated leuco-compounds may be treated in this manner or the condensation of the leuco-hydroxyanthraquinone with the concentrated mono-ethanolamine and the formation of. the dyestufl may occur .in a

single operation which" is of great practical advantage." E x 1 1 Inucontrast" with the processes zhitherto known, the new Y process has the] advantage that ituses neither costlymaterials for the oxidation nor solvents which must be regen erated; the products obtained are distinguished to a surprising extent from those which are made by oxidation according to the aforesaid specifications by the extraordinarly1 purity of the dyeing tints which they .yie I ,The followingexamples illustrate the invention' the parts being by weights-- Example 1 10 partsof the :leuco-derivative obtained by reaction of leuco-1z4z5:8-tetrahydroxy-v anthraquinone -of'the formula Y I 1 -0H0H0H I v OH H 11 with an alcoholic solution ofmonoethanolaminelare heated-with access of air in 50 parts of pure monoethanolamine for 3 hours at, 50-60 ;C.1-Tlle violet: brown: color changes very rapidlyinto a blue-green. The

dyestuff of theformula a v on r NH-GzHr-OH Y I I v Nil-01114 03- g I d i m -ogm-on I is obtained which dyes acetate silk extraordinarily pure blue tints.

1 Ewample 2 10 parts of leuco-lz4z5:S-tetrahydroxyanthraquinone are heated with parts of monoethanolamine with access of air at 50- C. for 3 hours. The mixture is worked up as described in Example 1 and the pure product of the formula is thus obtained from the leuco-derivative in one operation.

What we claim is 1. "Process for the manufacture of hydroxyethylamino-derivatives of the anthraquinone series, consisting in heating the leuco-derivatives of the general formula wherein m in both cases stands for H or OH, with access of oxygen in presence of con- T centrated products of the reaction of ethylene-oxide with ammonia.

2. Process for the manufacture of hydroxyethylamino-derivatives of the anthraquinone series, consisting in heating the leuco-derivatives of the general formula wherein in both cases stands for H or OH, with access of oxygen in presence of concentrated monoethanolamine.

Y with access of oxygen in 3. Process for the manufacture of a hydroxyethylamino-derivative of the anthraquinone series, consisting in heating the leuco-derivative of the formula OH OH NH-O2H4OH tn H NH-C2H4OH with access of oxygen in presence of concentratedmonoethanolamine. T 4. A IIIOdIfiCa-tIOII- 'Of the process 'of clalm 1, consisting in heating leuco-deriyatives of the general formula a: OH OH x KBHbH wherein m in both cases stands for-H or OH, with access of oxygen in presence of concentrated products of the reaction of ethylene-oxidewith ammonia.

5. A modification of the process of claim 2, consisting in heating leuco derivatives of the general formula z OH on I OH" I OH wherein m 'in'both'cases stands for H orOH,

presence of concentrated monoethanolamine. i

6. A modification of theprocess of claim 3, consisting in heating a leuco-deriyativeof the formula OH on on I H on on with access of oxygen inpresence of concentrated monoethanolamine.

7. The hydroxyethylaminoederivatiyes of. the anthraquinone series of; the generalforg wherein a: inboth cases stands for H or OH,

obtained by heating the leuco-derivatives of the general formula wherein an in both cases stands for H or OH, with access of oxygen in presence of concentrated products of the reaction of ethylene-oxide with ammonia, which products dye acetate silk blue green to green blue tints of a purity not hitherto reached.

8. The hydroxyethylamino-derivatives of the anthraquinone series of the general formula wherein m in both cases stands for'H or OH,

obtained by heating the leuco-derivatives of the general formula I on NH-CaHr-OH wherein m in both cases stands for H or OH, with access of oxygen in presence of concentrated monethanolamine, which products dye acetate silk blue green to green blue tints of a purity not hitherto reached.

9. The hydroxyethylamino-derivative of the anthraquinone series of the formula obtained by heating the leuco-derivative of the formula OH on NHC:H4OH

with access of oxygen in presence of concentrated monoethanolamine, which product dyes acetate silk a bluish green tint of a purity not hitherto reached.

In witness whereof we have hereunto signed our names this 13th day of Ma 1931.

HERMANN HAU ER. MAX BOMMER. 

